CN102093408B - Benzocyclobutene substituted annular siloxane monomer as well as preparation method and application of benzocyclobutene substituted cyclic annular siloxane monomer - Google Patents
Benzocyclobutene substituted annular siloxane monomer as well as preparation method and application of benzocyclobutene substituted cyclic annular siloxane monomer Download PDFInfo
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Abstract
The invention belongs to the technical field of micro-electronic packaging dielectric materials, particularly relates to a benzocyclobutene (BCB) substituted annular siloxane monomer as well as preparation and an application of the BCB substituted annular siloxane monomer. Annular vinyl siloxane and 4-benzocyclobutene are reacted in one step in the presence of a palladium catalyst so as to obtain a target monomer; and the monomer can be directly heated for polymerization forming, or the monomer also can be prepared into an organic solution of prepolymer and then spin film making is carried out on base plate materials such as metal, ceramic, silicon and the like. The preparation and use methods of the BCB substituted annular siloxane monomer are simple and convenient, the resins subjected to heat curing have the advantages of high stability, low dielectric constant, low dielectric loss, low water absorption and good film forming property, can be used as a high property dielectric material, and has wide application prospects in the fields of electronic packaging, system integration and the like.
Description
Technical field
The invention belongs to microelectronics Packaging dielectric material technical field, be specially siloxanyl monomers of benzocyclobutene substituted cyclic more than a type and preparation method thereof and application.
Background technology
Along with electronic product to gentlier, the continuous pursuit of thinner, littler, high-performance, reduce power consumption; Mcm (Multichip Module; Be called for short MCM), advanced encapsulation technologies such as disk stage packaging (Wafer Level Package is called for short WLP), three-dimension packaging have obtained widespread use, thereby have dwindled the volume of electronic system significantly in the electronic devices and components manufacturing; Alleviate weight, improved safety.The core of MCM technology is the multilayer wiring on base plate for packaging, and wherein dielectric is very crucial material, and it has determined performance and the safety of MCM to a great extent.Polyimide (PI) is a kind of MCM dielectric material commonly used, but have water absorbability big (0.5% ~ 1.7%), planarity is poor, solidification value is high (greater than 280 ℃), shrinking percentage shortcomings such as (about 25%) greatly.Since the nineties, people are devoted to study a kind of novel medium material----benzocyclobutene (Benzocyclobutene is called for short BCB) resin, and its structural formula is shown in I, and systematic naming method is a dicyclo [4,2,0]-1,3, the 5-triolefin.BCB is considered to the SiO that continues
2, the silicon substrate MCM dielectric material of new generation after the polyimide, in disk stage packaging and three-dimension packaging, also obtained widespread use.
The BCB resin that is adopted in the Electronic Packaging; Contain two BCB groups in the monomer whose molecular structure mostly; General formula of molecular structure is shown in II, and the kind of R functional group influences monomeric physical properties consumingly, such as heat of polymerization of solubility, fusing point and the every gram of monomer etc.; The structure of R functional group also gives the BCB resin certain function simultaneously, like photosensitivity, thermoplasticity, thermoset etc.At present; Mostly the BCB resin that is adopted in the microelectronics Packaging is to contain the divalence connecting group of reactive unsaturated group; Like Dow company at U. S. Patent 4812588; U. the DVS-BCB resin of being reported in the patent such as S. Patent 5138081; Compare with polyimide commonly used; This material have specific inductivity low (frequency 1kHz-1MHz scope in time be 2.7), water-intake rate low (< 0.25%), high-frequency dielectric loss little (dielectric loss of PI when 1kHz is 0.002, the dielectric loss of DVS-BCB resin in the 1kHz-1MHz scope all less than 0.0008), solidification value low (from the several seconds several hours to 300 ℃ time the under 200 ℃ of temperature) and with character such as the compatibility of various metal layers is good.In addition; The vinyl of introducing on the molecular chain makes it have sensitivity of light; Utilize DVS-BCB can directly form images, and need not use means such as plasma etching or laser-induced thermal etching, thereby reach the purpose that reduces process step, saves manufacturing cost through exposure imaging as the dielectric material.This material has been widely used in high-end microelectronic, comprises the embedding technology of multilayer wiring, IC stress buffer/>passivation layer, Flip-Chip Using, CSP encapsulation, high-frequency element and passive element etc., becomes application BCB resin the most widely.
Ⅰ Ⅱ 。
Summary of the invention
The object of the present invention is to provide cyclic monomer that contains a plurality of benzocyclobutene groups of one type of preparation convenience, excellent performance and preparation method thereof, and the application of above-mentioned synthon.
Shown in the following formula III of structure of many benzocyclobutenes substituted cyclic siloxanyl monomers that the present invention proposes:
Ⅲ 。
The n value is 1 or 2.
When n=1, the compound molecule formula is C
33H
36O
3Si
3, Chinese: 1,3; 5-trimethylammonium-1,3,5-three (2 '-(4 '-benzocyclobutane thiazolinyl) vinyl) cyclotrisiloxane; English name: 1,3,5-trimethyl-1; 3,5-tri [2 '-(4 '-benzocyclobutenyl)] vinylcyclotrisiloxane, be designated as: cyclotrisiloxane BCB.
When n=2, the compound molecule formula is C
44H
48O
4Si
4, Chinese: 1,3,5,7-tetramethyl--1; 3,5,7-four (2 '-(4 '-benzocyclobutane thiazolinyl) vinyl) cyclotetrasiloxane, English name: 1; 3,5,7 ,-tetramethyl-1; 3,5,7-tetra [2 '-(4 '-benzocyclobutenyl)] vinylcyclotetrasiloxane, be designated as: cyclotetrasiloxane BCB.
The preparation method of many benzocyclobutene monomers that the present invention proposes is following: under alkali and catalyst action, obtain target molecule through single step reaction by methyl ethylene annular siloxane and 4-bromobenzene and cyclobutene, reaction formula is as follows:
Concrete steps are: with methyl ethylene annular siloxane shown in the formula (IV), 4-bromobenzene and cyclobutene, alkali, catalyzer, catalyst ligand and solvent, mixture under protection of inert gas in 60-90 ℃ of stirring reaction 20-30 hour, then with in the reactant impouring aqueous hydrochloric acid; Mixed solution is used organic solvent extraction, aqueous phase discarded, and the organic phase water is washed till neutrality; Anhydrous magnesium sulfate drying after organic solvent is removed in filtration, evaporation, obtains yellowish brown oily matter; Through silica gel column chromatography; Leacheate is removed in underpressure distillation, obtains faint yellow thickness product (seeing (III) formula), productive rate 40-65%.
Wherein, the mol ratio of reactant annular siloxane and 4-bromobenzene and cyclobutene is 1: 3-3.5 (n=1) or 1: 4-4.5 (n=2); Catalyzer is a kind of of palladium metal salt, and like palladium, Palladous chloride etc., catalyst levels is the 1-5% mole of reactant 4-bromobenzene and cyclobutene; Catalyst ligand is triphenylphosphine or three (o-methyl-phenyl-) phosphine, and its consumption is 1-5 a times of catalyst levels; Used alkali is that organic bases (like triethylamine or 1,2,2,6,6-pentamethyl-piperidines etc.) or mineral alkali are (like Na
2CO
3, K
2CO
3Or NaOAc etc.) a kind of, its consumption be 4-bromobenzene and cyclobutene 1-3 doubly; Solvent can be among DMF, THF, acetonitrile, the DMA a kind of, solvent load is that every gram 4-bromobenzene and cyclobutene add the 2-5 milliliter.Extraction uses organic solvent to be normal hexane, CH
2Cl
2, CHCl
3, benzene or toluene a kind of.The selected leacheate of silica gel column chromatography is sherwood oil-dichloromethane mixture, and volume ratio is 8-15:1.
The present invention also provides above-mentioned ring-type BCB monomer (formula III; N=1; 2) method of use: at first above-mentioned synthetic monomer (formula III) and organic solvent are mixed with the solution that massfraction is 15-60 wt%, wherein organic solvent is a kind of in sym-trimethylbenzene, YLENE, the phenyl ether.Then this solution is being fit to the prepolymer that temperature (160-180 ℃) obtained ring-type BCB in refluxed 20-80 hour, this prepolymer need not to handle, can be on material surfaces such as silicon chip, metal, pottery, polymkeric substance direct spin coating system film, 200-300 ℃ of curing.
After solidifying, the cyclic monomer that the present invention obtains contains a plurality of benzocyclobutene groups has following characteristics: high thermal stability, low-k and dielectric loss, low water absorption and good film-forming properties etc.Because monomer itself has bigger molecular weight, therefore when the prepolymer solution of preparation specified molecular weight, required time is short, and efficient is high.
Many benzocyclobutenes that the present invention obtains replace the siloxanes cyclic monomer and can be used as the high-performance dielectric materials with its performed polymer, in fields such as the Electronic Packaging and the system integration, have broad application prospects.
Description of drawings
Fig. 1 is the thermogravimetric analysis curve after cyclotetrasiloxane BCB (n=2) solidifies.
Fig. 2 is the AFM photo of cyclotetrasiloxane BCB (n=2) spin-coating film.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1 cyclotetrasiloxane BCB is monomeric synthetic: with 4-bromobenzene and cyclobutene (15.1g; 0.083mol), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (7.05g; 0.02mol), triethylamine (15ml), acetonitrile (50ml), palladium (334mg, 1.49mmol) (750mg 2.45mmol) adds in the 100mL three-necked flask with three (o-methyl-phenyl-) phosphine; Logical nitrogen drip washing began heating and stirs under the normal temperature after 30 minutes, in 85 ℃ of refluxed 24 hours.Finish reaction, be cooled to room temperature, impouring 150mL concentration is in the aqueous hydrochloric acid of 1mol/L, 150mL (3*50mL) dichloromethane extraction, and organic phase is extremely neutral with washing (5*150mL).Anhydrous magnesium sulfate drying spends the night, and filters, and removes dichloromethane solution and obtains pale brown look oily matter.Purification by silica gel column chromatography, leacheate: sherwood oil (boiling range 60-90 ℃)/methylene dichloride=10/1 (v/v), underpressure distillation obtains faint yellow thickness product 7.6 g (productive rate 48.4%) after removing solvent.
1H-NMR(500MHz, CD
3COCD
3,δ)：0.26-0.32(12 H，CH
3)，3.05-3.17(16 H，-CH
2CH
2-)，6.22-6.30(4 H，CH=CH)，6.89-6.98(4 H，CH=CH)，7.02-7.23(12 H, ArH)。IR(KBr, cm
-1): 2959(s), 2928(s), 2827(s), 1606(vs), 1578(s), 1472(s), 1254(vs), 1197(s), 1040(vs), 987(s), 848(s), 803(s)。
The preparation of embodiment 2 cyclotetrasiloxane BCB performed polymers: 1 synthetic cyclotetrasiloxane of embodiment BCB monomer (2.43g) is joined in sym-trimethylbenzene (7.52g) solvent; In 160 ℃ ~ 170 ℃ refluxed 24 hours; Be cooled to room temperature, obtain directly to be used for the pre-polymer solution of spin coating system film.Gel osmoticing chromatogram analysis shows that this prepolymer number-average molecular weight is 3596g/mol, and weight-average molecular weight is 4135g/mol, and MWD is 1.150.
The curing of embodiment 3 cyclotetrasiloxane BCB: BCB puts into specific mould with 1 synthetic cyclotetrasiloxane of embodiment; React according to following condition: 80 ℃/1h; 150 ℃/1h, 210 ℃/1h, 240 ℃/1h; 250 ℃/1h, obtain the cured resin that pore-free distributes and has mechanical property.IR(KBr, cm
-1): 2958 (s)，2925(s), 2827(s), 1604(s), 1570(m), 1500(s), 1437(s), 1261(vs), 1059(vs), 788(s)。Thermogravimetric analysis: the initial heat decomposition temperature of cyclotetrasiloxane BCB cured product (1% weightlessness) is 487.3 ℃, and the residual volume in the time of 600 ℃ is 65.1%.
The preparation of embodiment 4 cyclotetrasiloxane BCB films: the sym-trimethylbenzene drips of solution of the cyclotetrasiloxane BCB performed polymer that 1mL embodiment 2 is prepared is on the silicon chip that cleaning surfaces is crossed; With 2500 rev/mins speed spin coatings 30 seconds; Solidify according to following condition: 210 ℃/1h; 240 ℃/1h, 250 ℃/1h, obtain cyclotetrasiloxane BCB cured film.AFM analysis revealed, thickness are that its average surface roughness of cured film of 1.87 microns is 0.3 nanometer, and r.m.s. roughness is 0.4 nanometer, and surperficial maximum difference of height is 3.4 nanometers.
Claims (15)
1. the siloxanyl monomers of benzocyclobutene substituted cyclic more than a type is characterized in that structure is following:
Wherein, the n value is 1 or 2.
2. the preparation method of many benzocyclobutenes substituted cyclic siloxanyl monomers as claimed in claim 1 is characterized in that concrete steps are: with methyl ethylene annular siloxane, 4-bromobenzene and cyclobutene, alkali, catalyzer, catalyst ligand and solvent, mixture under protection of inert gas in 60-90 ℃ of stirring reaction 20-30 hour; Then with in the reactant impouring aqueous hydrochloric acid; Mixed solution is used organic solvent extraction, aqueous phase discarded, and the organic phase water is washed till neutrality; Anhydrous magnesium sulfate drying; Filter, remove organic solvent after, through purification by silica gel column chromatography;
Wherein, described catalyzer is Palladous chloride or palladium; Said catalyst ligand is triphenylphosphine or three (o-methyl-phenyl-) phosphine.
3. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that: n=1, and the mol ratio of methyl ethylene annular siloxane and 4-bromobenzene and cyclobutene is 1: 3 ~ 3.5; N=2, the mol ratio of methyl ethylene annular siloxane and 4-bromobenzene and cyclobutene is 1: 4 ~ 4.5.
4. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that described catalyst levels is 4-bromobenzene and cyclobutene 1 ~ 5% mole.
5. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2, the consumption that it is characterized in that said catalyst ligand is a 1-5 times of mole of said catalyst levels.
6. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that said alkali is a kind of in organic bases or the mineral alkali.
7. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that the 1-3 times of mole that said alkali consumption is 4-bromobenzene and cyclobutene.
8. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that said solvent is N, a kind of in dinethylformamide, DMAC N,N, THF or the acetonitrile.
9. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that solvent load is that every gram 4-bromobenzene and cyclobutene add 2-5 milliliter solvent.
10. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that said extraction uses organic solvent to be normal hexane, CH
2Cl
2, CHCl
3, benzene or toluene.
11. many benzocyclobutenes substituted cyclic siloxanyl monomers preparation method according to claim 2 is characterized in that said silica gel column chromatography solvent for use is sherwood oil and/or methylene dichloride.
12. the method for use of many benzocyclobutenes substituted cyclic siloxanyl monomers as claimed in claim 1; It is characterized in that: described many benzocyclobutenes substituted cyclic siloxanyl monomers and organic solvent are hybridly prepared into mixing solutions; Then with this mixing solutions in the proper temperature refluxed; Obtain many benzocyclobutenes substituted cyclic siloxane prepolymer, with this prepolymer direct spin coating system film on material surface; Said organic solution concentration is 15-60 wt%, and return time is 20-80 hour, and reflux temperature is 160-180 ℃.
13. many benzocyclobutenes substituted cyclic siloxanyl monomers method of use according to claim 12 is characterized in that said organic solvent is a kind of in sym-trimethylbenzene, YLENE, the phenyl ether.
14. many benzocyclobutenes substituted cyclic siloxanyl monomers method of use according to claim 12 is characterized in that many benzocyclobutenes substituted cyclic siloxanyl monomers or its performed polymer, solidifies down at 200-300 ℃.
15. many benzocyclobutenes substituted cyclic siloxanyl monomers according to claim 1 is characterized in that the application as the dielectric substance in the Electronic Packaging, heat interfacial material and mechanical connection material of this monomer or its performed polymer.
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| CN102915956B (en) * | 2012-09-12 | 2016-01-13 | 复旦大学 | Silicon through-hole wall makes the method for benzocyclobutene resin dielectric layer |
| CN103788123B (en) * | 2012-11-02 | 2017-04-12 | 北京化工大学 | Bifunctional benzoxazine resin containing twin-tower silsesquioxane |
| CN103665025B (en) * | 2013-12-31 | 2016-07-06 | 复旦大学 | The synthetic method of adamantyl benzocyclobutene monomer and polymer thereof |
| CN103762198B (en) * | 2013-12-31 | 2016-07-06 | 中国科学院微电子研究所 | A kind of TSV filling perforation method |
| CN110540648A (en) * | 2014-11-07 | 2019-12-06 | 中国科学院上海有机化学研究所 | Organic siloxane containing benzocyclobutene group and preparation and application thereof |
| CN108516986B (en) * | 2018-05-16 | 2020-11-17 | 西南科技大学 | Benzocyclobutene-functionalized tetrakis (dimethylsiloxy) silane, method for preparing same, and method for preparing resin containing same |
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| US5138081A (en) * | 1991-04-30 | 1992-08-11 | The Dow Chemical Company | Process for purifying vinylically-unsaturated organosilicon compounds |
| CN1495866A (en) * | 2002-08-30 | 2004-05-12 | �����ɷ� | Semiconductor device and its making method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138081A (en) * | 1991-04-30 | 1992-08-11 | The Dow Chemical Company | Process for purifying vinylically-unsaturated organosilicon compounds |
| CN1495866A (en) * | 2002-08-30 | 2004-05-12 | �����ɷ� | Semiconductor device and its making method |
Non-Patent Citations (1)
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